CN108483684A - 一种高含硫油田采出水处理阻垢缓蚀剂 - Google Patents

一种高含硫油田采出水处理阻垢缓蚀剂 Download PDF

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CN108483684A
CN108483684A CN201810196078.3A CN201810196078A CN108483684A CN 108483684 A CN108483684 A CN 108483684A CN 201810196078 A CN201810196078 A CN 201810196078A CN 108483684 A CN108483684 A CN 108483684A
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corrosion inhibitor
incrustation corrosion
water treatment
water
high sulfur
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CN108483684B (zh
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闫旭涛
王丽莉
朱瑞龙
南粉益
姚彬
张玉荣
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Shaanxi Chemical Research Institute Co ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • C02F5/145Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus combined with inorganic substances
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/105Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances combined with inorganic substances
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/185Refractory metal-containing compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/08Corrosion inhibition

Abstract

本发明公开了一种高含硫油田采出水处理阻垢缓蚀剂,其质量百分配比组成为:有机膦酸盐25%~40%、丙烯酸‑丙烯酸羟丙酯共聚物15%~25%、钼酸盐或钨酸盐2.5%~5%、氢氧化钠5%~9%、可溶性锰盐0.5%~3.0%,余量为水。本发明阻垢缓蚀剂是用于油田采出水处理系统,抑制采出水的结垢和腐蚀,投加量为20~50mg/L,阻垢率>95.8%,腐蚀速率<0.076mm/a,具有用量少、阻垢缓蚀效果好的优点,且其pH值范围为6.0~8.0,属于中性药剂,对加药系统、注水设备及注水管线的腐蚀性小,且投加后不会引起待处理水质的pH值波动。本发明阻垢缓蚀剂的成本低,制备工艺简单,原料易得,减少了除氧剂、除硫剂的投加,能较好的控制高含硫油田采出水产生的腐蚀。

Description

一种高含硫油田采出水处理阻垢缓蚀剂
技术领域
本发明属于水处理技术领域,具体涉及一种高含硫油田采出水阻垢缓蚀剂。
背景技术
目前我国大部分油田已进入注水开发阶段,注水主要来源于油田采出水,油田采出水处理后回注地层,既满足了油田生产的需要,同时也保护了环境资源,为油田带来了巨大的经济和社会效益。油田采出水水温高、矿化度大,含有大量的钙、镁、钡、锶等成垢金属离子及CO2、H2S、O2等腐蚀性气体和SO4 2-、Cl-等腐蚀性离子,极易引起水处理设备、注水井套管和注水泵及输水管线的结垢和腐蚀,造成注水压力升高,注水效率下降,甚至造成输水管线的穿孔及油田污水的泄露,影响了油田的正常生产,尤其是采出水中高浓度硫化物会加剧采出水的腐蚀。油田采出水中富含溶解氧,在pH值5.5-8.5左右,溶解氧是引起金属腐蚀的主要因素之一,硫离子含量高会加剧腐蚀,而溶解氧和硫离子在一般条件下反应很缓慢,在油田水中可以较长时间共存。为了解决结垢和腐蚀问题,油田通用的做法是向采出水处理系统投加除氧剂、脱硫剂、阻垢剂及缓蚀剂等多种药剂,但目前油田采出水处理系统所用的阻垢缓蚀剂用量偏大,一般要大于50mg/L,且溶液多为酸性液体,易于对加药系统造成腐蚀。
发明内容
本发明的目的在于克服现有技术存在的缺点,解决结垢和腐蚀问题投加多种药剂和多种药剂的配伍性问题,以及酸性阻垢缓蚀剂对加药系统造成腐蚀等隐患,提供一种高效的油田采出水处理阻垢缓蚀剂,能够在高硬度、高含硫量的强腐蚀性水质条件下防止油田注水系统的结垢和腐蚀。
实现上述目的采用的阻垢缓蚀剂由下述质量百分配比的原料组成:
上述的高含硫油田采出水处理阻垢缓蚀剂优选由下述质量百分配比的原料组成:
上述的有机膦酸盐为2-膦酸丁烷-1,2,4-三羧酸或氨基三甲叉膦酸;所述丙烯酸-丙烯酸羟丙酯共聚物的质量指标中pH(1%溶液)=7.5±1.0;所述的钨酸盐为钨酸钠,钼酸盐为钼酸钠;所述的可溶性锰盐为硫酸锰或氯化锰。
本发明缓蚀阻垢剂的制备方法为:按照上述原料的质量百分配比,将水加热到25~35℃,缓慢加入可溶性锰盐,待其完全溶解后,溶解钼酸盐或钨酸盐,然后依次加入有机膦酸盐、丙烯酸酯共聚物,搅拌15~25分钟,然后缓慢加入氢氧化钠,搅拌20~30分钟,得到澄清透明液体,冷却至室温,即为成品。
本发明采用可溶性锰盐可以加速硫离子的氧化,从而消除了采出水中硫离子和溶解氧引起的腐蚀因素;钼酸盐或钨酸盐为缓蚀助剂,2-膦酸丁烷-1,2,4-三羧酸或氨基三甲叉膦酸是阻垢的主要成分,也有缓蚀效果;丙烯酸-丙烯酸羟丙酯共聚物是阻垢助剂,氢氧化钠是作为稳定剂,2-膦酸丁烷-1,2,4-三羧酸或氨基三甲叉膦酸中加入丙烯酸-丙烯酸羟丙酯共聚物,溶液会变浑浊,加入氢氧化钠可使溶液重新澄清,且溶液pH值6.5~7.5比较稳定。
本发明具有以下有益效果:
1、本发明阻垢缓蚀剂是用于油田采出水处理系统,抑制采出水的结垢和腐蚀,用于油田采出水处理系统的投加量为20mg/L~50mg/L,具有用量少、阻垢缓蚀效果好的优点,阻垢率>95.8%,腐蚀速率<0.076mm/a。
2、本发明阻垢缓蚀剂的pH值范围为6.0~8.0,属于中性药剂,对加药系统、注水设备及注水管线的腐蚀性小,且投加后不会引起待处理水质的pH值波动。
3、本发明阻垢缓蚀剂的成本低,制备工艺简单,原料易得。
4、本发明阻垢缓蚀剂减少了除氧剂、除硫剂的投加,能较好的控制高含硫油田采出水产生的腐蚀。
具体实施方式
下面结合实施例对本发明进一步详细说明,但本发明的保护范围不仅限于这些实施例。
实施例1
以制备100g阻垢缓蚀剂为例,其原料的质量组成如下:
其制备方法为:将31.8g水加热到25~35℃,缓慢加入1.2g氯化锰,待其完全溶解后,溶解4g钼酸盐或钨酸盐,然后依次加入35g 2-膦酸丁烷-1,2,4-三羧酸、22g丙烯酸-丙烯酸羟丙酯共聚物,搅拌20分钟,然后缓慢加入6g氢氧化钠,搅拌30分钟,得到澄清透明液体,冷却至室温,即为油田采出水处理复合阻垢缓蚀剂。
实施例2
以制备100g阻垢缓蚀剂为例,其原料的质量组成如下:
其制备方法与实施例1相同。
实施例3
以制备100g阻垢缓蚀剂为例,其原料的质量组成如下:
实施例4
以制备100g阻垢缓蚀剂为例,其原料的质量组成如下:
其制备方法与实施例1相同。
为了证明本发明的有益效果,发明人对实施例1~4制备的阻垢缓蚀剂的性能进行了评价,具体如下:
1、阻垢性能
碳酸钙的阻垢性能参照SY/T 5673-93《油田用防垢剂性能评定方法》进行测试,试验温度70±2℃,时间25h,静态阻垢性能测定结果见表1。
表1阻垢性能测试结果
序号 阻垢缓蚀剂投加量/(mg·L-1) CaCO3阻垢率/%
实施例1 30 97.6
实施例2 30 99.1
实施例3 30 96.2
实施例4 30 98.3
由表1结果可知,本发明实施例1~4的阻垢缓蚀剂对CaCO3的阻垢效果好,加入量30mg/L时阻碳酸钙的阻垢率均大于96.0%。
2、缓蚀性能测试
缓蚀性能参照SY/T5273-2000《油田采出水用缓蚀剂性能评价方法》,实验条件:温度50℃,时间120h,试片:Q235钢,旋转速率100r/min,实验介质:延长油田某联合站油田采出水,水质情况见表2。缓蚀性能测定结果见表3。
表2延长油田某联合站油田采出水水质
项目 结果
Na+,mg/L 16290
K+,mg/L 149
Ca2+,mg/L 2960
Mg2+,mg/L 651
HCO3 -,mg/L 528
SO4 2-,mg/L 960
Cl-,mg/L 23880
含油量,mg/L 0.39
悬浮物,mg/L 1.26
含硫量,mg/L 21.8
pH值 6.9
表3腐蚀试验结果
序号 阻垢缓蚀剂投加量/(mg·L-1) 腐蚀速率/(mm·a-1)
实施例1 30 0.0359
实施例2 30 0.0287
实施例3 30 0.0215
实施例4 30 0.0306
由表3可见,本发明实施例1~4的阻垢缓蚀剂的动态腐蚀速率均小于SY/T5329-1994腐蚀速率0.076mm/a的标准。

Claims (4)

1.一种高含硫油田采出水处理阻垢缓蚀剂,其特征在于该阻垢缓蚀剂由下述质量百分配比的原料组成:
上述的有机膦酸盐为2-膦酸丁烷-1,2,4-三羧酸或氨基三甲叉膦酸;所述丙烯酸-丙烯酸羟丙酯共聚物的质量指标中1%溶液的pH=7.5±1.0。
2.根据权利要求1所述的高含硫油田采出水处理阻垢缓蚀剂,其特征在于该阻垢缓蚀剂由下述质量百分配比的原料组成:
3.根据权利要求1或2所述的高含硫油田采出水处理阻垢缓蚀剂,其特征在于:所述的钨酸盐为钨酸钠,钼酸盐为钼酸钠。
4.根据权利要求1或2所述的高含硫油田采出水处理阻垢缓蚀剂,其特征在于:所述的可溶性锰盐为硫酸锰或氯化锰。
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